This invention relates to alkaline earth silicate fibres.
Inorganic fibrous materials are well known and widely used for many purposes (e.g. as thermal or acoustic insulation in bulk, mat, or blanket form, as vacuum formed shapes, as vacuum formed boards and papers, and as ropes, yarns or textiles; as a reinforcing fibre for building materials; as a constituent of brake blocks for vehicles). In most of these applications the properties for which inorganic fibrous materials are used require resistance to heat, and often resistance to aggressive chemical environments.
Inorganic fibrous materials can be either glassy or crystalline. Asbestos is an inorganic fibrous material one form of which has been strongly implicated in respiratory disease.
It is still not clear what the causative mechanism is that relates some asbestos with disease but some researchers believe that the mechanism is mechanical and size related. Asbestos of a critical size can pierce cells in the body and so, through long and repeated cell injury, have a bad effect on health. Whether this mechanism is true or not regulatory agencies have indicated a desire to categorise any inorganic fibre product that has a respiratory fraction as hazardous, regardless of whether there is any evidence to support such categorisation. Unfortunately for many of the applications for which inorganic fibres are used, there are no realistic substitutes.
Accordingly there is a demand for inorganic fibres that will pose as little risk as possible (if any) and for which there are objective grounds to believe them safe.
A line of study has proposed that if inorganic fibres were made that were sufficiently soluble in physiological fluids that their residence time in the human body was short; then damage would not occur or at least be minimised. As the risk of asbestos linked disease appears to depend very much on the length of exposure this idea appears reasonable. Asbestos is extremely insoluble.
As intercellular fluid is saline in nature the importance of fibre solubility in saline solution has long been recognised. If fibres are soluble in physiological saline solution then, provided the dissolved components are not toxic, the fibres should be safer than fibres which are not so soluble. Alkaline earth silicate fibres have been proposed for use as saline soluble, non-metallic, amorphous, inorganic oxide, refractory fibrous materials. The invention particularly relates to glassy alkaline earth silicate fibres having silica as their principal constituent.
International Patent Application No. WO8705007 disclosed that fibres comprising magnesia, silica, calcia and less than 10 wt % alumina are soluble in saline solution. The solubilities of the fibres disclosed were in terms of parts per million of silicon (extracted from the silica containing material of the fibre) present in a saline solution after 5 hours of exposure. WO8705007 stated that pure materials should be used and gave an upper limit of 2 wt % in aggregate to the impurities that could be present. No mention of alkali metals was made in this patent.
International Patent Application No. WO8912032 disclosed additional fibres soluble in saline solution and discusses some of the constituents that may be present in such fibres. This disclosed the addition of Na2O in amounts ranging from 0.28 to 6.84 wt % but gave no indication that the presence of Na2O had any effect.
European Patent Application No. 0399320 disclosed glass fibres having a high physiological solubility and having 10-20 mol % Na2O and 0-5 mol % K2O. Although these fibres were shown to be physiologically soluble their maximum use temperature was not indicated.
Further patent specifications disclosing selection of fibres for their saline solubility include for example European 0412878 and 0459897, French 2662687 and 2662688, PCT WO8604807, WO9002713, WO9209536, WO9322251, WO9415883, WO9716386 and U.S. Pat. No. 5,250,488.
The refractoriness of the fibres disclosed in these various prior art documents varies considerably and for these alkaline earth silicate materials the properties are critically dependent upon composition.
As a generality, it is relatively easy to produce alkaline earth silicate fibres that perform well at low temperatures, since for low temperature use one can provide additives such as boron oxide to ensure good fiberisation and vary the amounts of the components to suit desired material properties. However, as one seeks to raise the refractoriness of alkaline earth silicate fibres, one is forced to reduce the use of additives since in general (albeit with exceptions) the more components are present, the lower the refractoriness.
WO9315028 disclosed fibres comprising CaO, MgO, SiO2, and optionally ZrO2 as principal constituents. Such fibres are frequently known as CMS (calcium magnesium silicate) or CMZS ((calcium magnesium zirconium silicate) fibres. WO9315028 required that the compositions used should be essentially free of alkali metal oxides. Amounts of up to 0.65 wt % were shown to be acceptable for materials suitable for use as insulation at 1000° C. WO9315028 also required low levels of Al2O3 (<3.97%).
WO9415883 disclosed a number of such fibres usable as refractory insulation at temperatures of up to 1260° C. or more. As with WO9315028, this patent required that the alkali metal oxide content should be kept low, but indicated that some alkaline earth silicate fibres could tolerate higher levels of alkali metal oxide than others. However, levels of 0.3% and 0.4% by weight Na2O were suspected of causing increased shrinkage in materials for use as insulation at 1260° C. The importance of keeping the level of alumina low was stressed is stressed in this document.
WO9716386 disclosed fibres usable as refractory insulation at temperatures of up to 1260° C. or more. These fibres comprised MgO, SiO2, and optionally ZrO2 as principal constituents. These fibres are stated to require substantially no alkali metal oxides other than as trace impurites (present at levels of hundredths of a percent at most calculated as alkali metal oxide). The fibres have a general composition
SiO265–86%MgO14–35%with the components MgO and SiO2 comprising at least 82.5% by weight of the fibre, the balance being named constituents and viscosity modifiers. Such magnesium silicate fibres may comprise low quantities of other alkaline earths. The importance of keeping the level of alumina low was stressed is stressed in this document.
WO2003059835 discloses certain calcium silicate fibres certain calcium silicate compositions for which fibres show a low reactivity with aluminosilicate bricks, namely:—                65%<SiO2<86%        MgO<10%        14%<CaO<28%        Al2O3<2%        ZrO2<3%        B2O3<5%        P2O5<5%        72%<SiO2+ZrO2+B2O3+5*P2O5 95%<SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5         
This patent also discloses the use of La2O3 or other lanthanide additives to improve the strength of the fibres and blanket made from the fibres. This patent application does not mention alkali metal oxide levels, but amounts in the region of ˜0.5 wt % were disclosed in fibres intended for use as insulation at up to 126° C. or more.
WO2003060016 claims a low shrinkage, high temperature resistant inorganic fiber having a use temperature up to at least 1330 C, which maintains mechanical integrity after exposure to the use temperature and which is non-durable in physiological fluids, comprising the fiberization product of greater than 71.25 to about 85 weight percent silica, 0 to about 20 weight percent magnesia, about 5 to about 28.75 weight percent calcia, and 0 to about 5 weight percent zirconia, and optionally a viscosity modifier in an amount effective to render the product fiberizable.
EP 1323687 claims a biosoluble ceramic fiber composition for a high temperature insulation material comprising 75-80 wt % of SiO2, 13-25 wt % of CaO, 1-8 wt % of MgO, 0.5-3 wt % of ZrO2 and 0-0.5 wt % of Al2O3, wherein (ZrO2+Al2O3) is contained 0.5-3 wt % and (CaO+MgO) is contained 15-26 wt %.
Alkaline earth silicate fibres have received a definition in the Chemical Abstract Service Registry [Registry Number: 436083-99-7] of:—                “Chemical substances manufactured in the form of fibers. This category encompasses substances produced by blowing or spinning a molten mixture of alkaline earth oxides, silica and other minortrace oxides. It melts around 1500° C. (2732° F.). It consists predominantly of silica (50-82 wt %), calcia and magnesia (18-43 wt %), alumina, titania and zirconia (<6 wt %), and trace oxides.”.        
This definition reflects European Health and Safety regulations which impose special labelling requirements on silicate fibres containing less than 18% alkaline earth oxides.
However as is clearly indicated in relation to WO2003059835, WO2003060016 and EP 1323687, the silica content of alkaline earth silicate fibres is increasing with the demand for higher use temperatures and this is leading to lower alkaline earth contents.
The present invention is applicable not only to alkaline earth silicate fibres in this narrow definition reflected in the Chemical Abstracts definition, but also to alkaline earth silicate fibres having lower levels of alkaline earth oxides.
Accordingly, in the present specification alkaline earth silicate fibres should be considered to be materials comprising predominantly of silica and alkaline earth oxides and comprising less than 10 wt % alumina [as indicated in WO8705007—which first introduced such fibres], preferably in which alumina, zirconia and titania amount to less that 6 wt % [as indicated in the Chemical Abstracts definition]. For regulatory reasons, preferred materials contain more than 18% alkaline earth metal oxides.
The prior art shows that for refractory alkaline earth silicate fibres, alkali metals have been considered as impurities that can be tolerated at low levels but which have detrimental affects on refractoriness at higher levels.